US5602292A - Catalyst for the hydroisomerization of long-chain n-paraffins and process for preparing it - Google Patents
Catalyst for the hydroisomerization of long-chain n-paraffins and process for preparing it Download PDFInfo
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- US5602292A US5602292A US08/449,957 US44995795A US5602292A US 5602292 A US5602292 A US 5602292A US 44995795 A US44995795 A US 44995795A US 5602292 A US5602292 A US 5602292A
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- catalyst
- paraffins
- hydroisomerization
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 230000002378 acidificating effect Effects 0.000 claims abstract description 13
- 150000002739 metals Chemical class 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 28
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- 229910052681 coesite Inorganic materials 0.000 claims description 14
- 229910052906 cristobalite Inorganic materials 0.000 claims description 14
- 229910052682 stishovite Inorganic materials 0.000 claims description 14
- 229910052905 tridymite Inorganic materials 0.000 claims description 14
- 229910018404 Al2 O3 Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000012188 paraffin wax Substances 0.000 claims description 9
- 230000001588 bifunctional effect Effects 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 2
- 238000002441 X-ray diffraction Methods 0.000 claims 1
- 239000001993 wax Substances 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 description 46
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 11
- 238000005336 cracking Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000005470 impregnation Methods 0.000 description 9
- 229910000510 noble metal Inorganic materials 0.000 description 9
- 239000010457 zeolite Substances 0.000 description 9
- 229910021536 Zeolite Inorganic materials 0.000 description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 7
- 238000006317 isomerization reaction Methods 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000007669 thermal treatment Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000000151 deposition Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 239000011959 amorphous silica alumina Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- YWUXIGHUBKWHRW-UHFFFAOYSA-N 5-methylpentadecane Chemical class CCCCCCCCCCC(C)CCCC YWUXIGHUBKWHRW-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910017900 NH4 F Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- -1 aluminum compound Chemical class 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002801 charged material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical class [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
- C10G65/043—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a change in the structural skeleton
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
-
- B01J35/60—
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/62—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing platinum group metals or compounds thereof
-
- B01J35/617—
-
- B01J35/633—
-
- B01J35/643—
-
- B01J35/647—
-
- B01J35/67—
Definitions
- the present invention relates to a bifunctional catalyst constituted by an amorphous silica and alumina gel, and one or more metals belonging to Group VIIIA, to the preparation of such a catalyst and to its use hydroisomerization of long-chain n-paraffins containing more than 15 carbon atoms.
- the waxes mainly constituted (>80% by weight) by n-paraffins containing more than 15 carbon atoms and solid at room temperature, must be converted into their corresponding branched isomers having a higher melting point than their linear isomers.
- n-C 16 paraffin has a melting point of 19° C., whilst its 5-methyl pentadecane isomer melts at -31° C.
- An effective hydroisomerization catalyst should anyway minimize the possible cracking and hydrocracking reactions, which are catalyzed by the same acidic sites, and have, as intermediates, the same carbocations useful for hydroisomerization. These side reactions cause the degradation of the molecule, with less valuable, ligther products being formed, which must be removed from the end product in order not to increase the volatility thereof; the need for such additional removal step obviously increases the general costs of the overall process.
- bifunctional catalysts were developed, catalysts which are provided with both acidic sites and hydro-dehydrogenation active sites. The acidity is given to the catalyst by the type of selected carrier, and its function exactly is supplying the catalysts with such an isomerizing property.
- the hydro-dehydrogenating activity is supplied to the catalyst by the deposited metal phase, the function of which is also of keeping cracking reactions to a very minimum.
- the effectiveness of various catalysts can be evaluated on model compounds as n-paraffins, by measuring the selectivity thereof, i.e., the ratio of the isomerization products to the cracking products, at a given level of conversion of n-paraffins.
- EP-A-321,307 discloses a process for wax hydroisomerization in order to produce lubricant oil bases, which implies a hydroisomerization step carried out in the presence of a particular catalyst.
- the latter contains from 0.1 to 5% by weight of a metal belonging to Group VI or VIIIA, preferably VIIIA, still more preferably a noble metal of Group VIIIA, in the most preferred form, platinum supported on a halogenated, preferably fluorinated, refractory inorganic oxide.
- the halogenation of the inorganic oxide is known to increase the acidity thereof.
- the surface acidity of fluorinated aluminas and their catalytic activity in the reactions occurring via carbocation is a function of their fluorine content (R. Covini, V. Fattore, N. Giordano, J. Catal., 1967, 9, 315-321).
- U.S. Pat. No. 4,975,17 discloses a further process for hydroisomerizing waxes, in which provided is a hydroisomerization step carried out in the presence of a catalyst constituted by beta zeolite plus one effective component in hydrogenation-dehydrogenation reaction, preferably a noble metal.
- This catalyst has a high SiO 2 :Al 2 O 3 ratio, at least equal to 30, preferably higher than 50, for example comprised within the range of from 100 to 500, in order to reduce the acidity thereof and consequently the possible cracking reactions.
- the catalyst disclosed in EP-A-321,307 suffers from the drawback that it should be prepared by starting from a highly toxic and corrosive reactant as HF, dissolved in water together with NH 4 F.
- the present invention relates to a bifunctional catalyst comprising:
- a carrier of acidic character constituted by an X-ray amorphous silica and alumina gel, with a molar ratio of SiO 2 :Al 2 O 3 comprised within the range of from 30:1 to 500:1, a surface area comprised with the range of from 500 to 1000 m 2 /g, with a porosity of from 0.3 to 0.6 ml/g, with a diameter of pores prevailingly comprised within the range of from 10 to 30 Angstroms;
- the acidic carrier of the present invention displays a ratio of SiO 2 :Al 2 O 3 comprised within the range of from 50:1 to 300:1 and a porosity of the order of 0.4-0.5 ml/g, and the noble metal, selected from platinum and palladium, is contained at a level of from 0.1 to 2% by weight.
- the silica and alumina gel can be advantageously prepared according to as disclosed in U.S. Pat. No. 5,049,536; in particular, an aqueous solution of a tetra alkyl ammonium hydroxide (TAA-OH), is prepared, in which "alkyl” means ethyl, n-propyl or n-butyl, of a soluble aluminum compound capable of yielding Al 2 O 3 by hydrolysis, and a soluble silicon compound capable of yielding SiO 2 by hydrolysis, with the amount of said constituents in said solution being such that the following molar ratios are complied with:
- TAA-OH tetra alkyl ammonium hydroxide
- the resulting solution is heated in order to cause it to undergo gelation; the resulting gel is dried and is calcined under an inert atmosphere and then under an oxidizing atmosphere.
- the metal phase can be added either by impregnation from an aqueous medium, or by ionic exchange.
- the silica-alumina gel prepared as disclosed above, is wetted with an aqueous solution of a compound of the selected noble matal, for example chloroplatinic acid or Pd(NH 3 ) 4 (NO 3 ) 2 , by operating at room or close-to-room temperatures, and at a pH value of the order of 1-4 pH units.
- a compound of the selected noble matal for example chloroplatinic acid or Pd(NH 3 ) 4 (NO 3 ) 2
- the solid material is dried, preferably in air, at room or close-to-room temperatures, and is submitted to a thermal treatment under an oxidizing atmosphere, preferably in air. Suitable temperatures for this thermal treatment are comprised within the range of from 200° to 600° C.
- Suitable temperatures for this thermal treatment are comprised within the range of from 200° to 600° C.
- the conditions are so adjusted that on silica-alumina particles an amount of noble metal is deposited which is comprised within the range of from 0.05 to 5% by weight, preferably of
- the silica-alumina gel is suspended in an aqueous solution of a noble metal complex or salt, for example, an aqueous solution of Pt(NH 3 ) 4 (OH) 2 or of Pt(NH 3 ) 4 Cl 2 or of Pd(NH 3 ) 4 (NO 3 ) 2 , by operating at room or close-to-room temperatures, and at a pH value comprised within the range of from 6 to 10.
- a noble metal complex or salt for example, an aqueous solution of Pt(NH 3 ) 4 (OH) 2 or of Pt(NH 3 ) 4 Cl 2 or of Pd(NH 3 ) 4 (NO 3 ) 2
- a noble metal complex or salt for example, an aqueous solution of Pt(NH 3 ) 4 (OH) 2 or of Pt(NH 3 ) 4 Cl 2 or of Pd(NH 3 ) 4 (NO 3 ) 2
- the solid matter is separated, then is washed with water, is dried and finally is submitted to thermal treatment in an inert
- bifunctional catalysts consist of silica-alumina gel carriers loaded with a noble metal, having in general a surface area comprised within the range of from 300 to 900 m 2 /g.
- those catalysts are however preferable which are prepared by means of the ionic exchange technique, and, among these, preferably those which contain palladium which, at low conversion rates, display very good selectivities to isoparaffins.
- the catalysts according to the present invention can be activated by drying and/or reduction, preferably by drying and subsequent reduction.
- the drying is carried out in an inert atmosphere at a temperature comprised within the range of from 100° to 400° C., and the reduction is obtained by means of the thermal treatment of the sample under a reducing atmosphere at temperatures comprised within the range of from 150° to 500° C.
- the catalysts according to the present invention can be used as such, or in combination with suitable inert, solid materials acting as binding agents.
- the catalyst and the binder can be mixed in mutual ratios, by weight, comprised within the range of from 30:70 to 90:10 and preferably of from 50:50 to 70:30.
- the above said two components can be bonded and compacted in their end desired shape, for example, as extrudates or pellets.
- the silica-alumina gel based catalyst loaded with a noble metal can be prepared by starting from the acidic carrier which already is an extrudate form.
- the carrier as a silica-alumina gel extrudate prepared according to the process disclosed in Italian patent application MI 91 A 003276 filed on Dec. 6th, 1991 is impregnated with a suitable aqueous solution of noble metal compound, then is dried and submitted to thermal treatment according to the same process as disclosed for the acidic carrier in powder form.
- the catalyst prepared according to the above reported techniques, as such, or bonded with an inert material, is active in the hydroisomerization process, which can be carried out either continuously or batchwise.
- the hydroisomerization is advantageously carried out in the presence of hydrogen, at a temperature comprised within the range of from 200° to 540° C., preferably of from 250° to 450° C., and under a pressure comprised within the range of from 25,000 kPa, preferably of from 4,000 to 10,000 kPa.
- the effective catalyst amount expressed as a percent content, by weight, based on the n-paraffin or mixtures of n-paraffins to be hydroisomerized, is generally comprised within the range of from 0.5 to 30% by weight, preferably of from 1 to 15% by weight.
- the material used as the acidic carrier in the catalysts claimed herein is prepared according to as disclosed in U.S. Pat. No. 5,049,536.
- TPA-OH tetrapropyl ammonium hydroxide
- TES tetraethyl silicate
- An X-ray amorphous silica-alumina gel is obtained in a quantitative yield relatively to the initial charged materials.
- the so prepared material is used as an acidic carrier on which platinum is deposited by means of an aqueous impregnation.
- an aqueous solution containing H 2 PtCl 6 (0.45% by weight/volume and (0.6M) HCl is added dropwise, with simultaneously carefully mixing.
- the reactants are kept into contact with each other for 16 hours, then water is evaporated off during 1 hour at the temperature of 60° C. in air and the sample is subsequently dried, during 2 hours, at 150° C., still in air.
- the calcination is carried out at 500° C. for 3 hours under a flowing air stream, with the muffle being heated from 23° to 500° C. during a 90 minutes time.
- the process is carried out with a carrier as from Example 1, by performing the metal phase deposition step by means of the ion exchange method.
- a catalyst is prepared by starting from a same carrier as from Example 1, by performing the metal phase deposition step by means of the ion exchange method.
- Example 2 grams of carrier as disclosed in Example 1 is added, with stirring at room temperature, to 1000 ml of demineraliized water. 27.23 ml of Pd(NH 3 ) 4 (NO 3 ) 2 (0.01M) and some drops of NH 4 OH at 35%, such as to increase the suspension pH up to about 6, are added; the resulting mixture is kept with stirring for 3 hours at room temperature. The resulting suspension is filtered, the filter cake is washed with water and is allowed to dry at room temperature. The drying takes place at a temperature of 80° C. in air for 3 hours, and the calcination is carried out at 250° C. for 3 hours, under a flowing air stream.
- a catalyst is prepared by starting from a same carrier as from Example 1, by performing the metal phase deposition step by means of the aqueous impregnation method.
- Example 1 A volume of 12.06 ml of an aqueous solution of Pd(NH 3 ) 4 (NO 3 ) 2 (0.005M) is added dropwise to 10 g of the same carrier as obtained from Example 1.
- the subsequent impregnation steps are carried out as in Example 1.
- the calcination is carried out at 250° C. during 3 hours under a flowing air stream with a temperature increase rate of 7° C./minute.
- a reference catalyst is prepared which is constituted by platinum supported on beta zeolite.
- Said beta zeolite is prepared under similar conditions to as disclosed i n U.S. Pat. No. 3,308,069.
- An amount of 59.8 g of an aqueous solution at 40% by weight/weight of tetraethylammonium hydroxide (TEA-OH) and 1.9 g of sodium aluminate are added to 58.4 g of demineralized water.
- the resulting mixture is heated up to about 80° C. and is kept with stirring until NaAlO 2 is completely dissolved.
- the crystallized product is filtered off, the filter cake is washed, is dried for 1 hour at 120° C., is calcined during 5 hours at 550° C. and is turned into its acidic form by exchange with ammonium acetate and subsequent calcination under the above indicated conditions.
- the Pt metal phase is deposited on the beta zeolite by aqueous impregnation.
- Example 1 The catalyst from Example 1 was tested in the reaction of hydroisomerization of n-C 16 paraffin, in a microautoclave, under the following conditions.
- the microautoclave is constituted by a steel body and a cover provided with a plurality of valves for pressurization, venting and optional recovery of gas products, and a pressure relief disk.
- the stirring system is constituted by a thin internal metal rod.
- the reactor is charged with 8 g of C 16 paraffin and 0.25 g of catalyst; the system is pressurized when cold with H 2 at 5 MPa and then is heated up to the temperature of 360° C.
- the point in time is considered when the temperature inside the reactor interior reaches the desired value.
- the reactor is cooled and the internal pressure thereof is relieved, and the reaction mixture is recovered.
- the analysis of the products in order to determine the conversion and their distribution is directly carried. out on the mixture, by gas chromatography (crosslinked methyl silicone gum HP-1 column, atomic emission detector).
- Example 2 A catalyst according to Example 2 is tested in the hydroisomerization of n-C 16 paraffins.
- the reaction conditions are the same as in Example 6.
- the values of conversion and selectivity are reported in Table 2.
- Example 3 A catalyst according to Example 3 is tested in the hydroisomerization of n-C 16 paraffins.
- the reaction conditions are the same as in Example 6.
- the values of conversion and selectivity are reported in Table 2.
- a catalyst according to Example 2 is tested in the hydroisomerization of n-C 16 paraffins.
- the reaction conditions are the same as in Example 7, except for the reaction time being extended to 240 minutes.
- the values of and selectivity are reported in Table 2.
- Example 5 The catalyst taken as the reference catalyst (Example 5) is tested in the hydroisomerization of n-C 16 paraffins.
- the reaction conditions are the same as in Example 6.
- the conversion rate and selectivity values are reported in Table 3.
- Example 5 The catalyst taken as the reference catalyst (Example 5) is tested in the hydroisomerization of n-C 28 paraffins.
- the reaction conditions are the same as in Example 6.
- the conversion rate and selectivity values are reported in Table 3.
- Example 1 A catalyst according to Example 1 is tested hydroisomerization of n-C 28 paraffins.
- the reaction conditions are the same as in Example 11.
- the values of conversion rate and selectivity are reported in Table 3.
- Examples 6 and 12 display a higher hydroisomerization selectivity, in the hydroisomerization of both n-C 16 and n-C 28 paraffins, with the operating conditions being the same, as compared to a catalyst taken as the reference catalyst (Examples 10 and 11).
- a catalyst as from Example 1 is tested in the hydroisomerization of n-C 16 paraffins.
- the reaction conditions are kept equal to those as of Example 6 in order to verify the reproducibility of the process.
- the values of conversion rate and selectivity are reported in Table 4.
- a catalyst as from Example 1 is first dried in an N 2 atmosphere at 300° C. and is subsequently tested in the hydroisomerization of n-C 16 paraffins.
- the reaction conditions are the same as of Example 6.
- the values of conversion and selectivity are reported in Table 4.
- a catalyst as from Example 1 is first activated under a H 2 atmosphere at 400° C. and is subsequently tested in the hydroisomerization of n-C 16 paraffins.
- the reaction conditions are the same as of Example 6.
- the values of conversion rate and selectivity are reported in Table 4.
- a catalyst as from Example 1 is first activated as in Example 15 and is subsequently tested in the hydroisomerization of n-C 16 paraffins.
- the reaction conditions are the same as of Example 15, except for the reaction time, which is reduced down to 60 minutes.
- the values of conversion and selectivity are reported in Table 4.
Abstract
Disclosed is an active catalyst in the hydroisomerization of waxes (paraffins), which catalyst is constituted by a carrier of acidic nature, of silica-alumina gel, and one or more metals belonging to Group VIIIA.
Also a process for preparing said catalyst is disclosed.
Description
This is a division of application Ser. No. 08/099,650 filed on Jul. 30, 1993 now abandoned.
The present invention relates to a bifunctional catalyst constituted by an amorphous silica and alumina gel, and one or more metals belonging to Group VIIIA, to the preparation of such a catalyst and to its use hydroisomerization of long-chain n-paraffins containing more than 15 carbon atoms.
The process of wax isomerization to yield lubricant oil bases characterized by a low pour point and by a high viscosity index, requires the use of suitable catalysts.
In fact, the waxes, mainly constituted (>80% by weight) by n-paraffins containing more than 15 carbon atoms and solid at room temperature, must be converted into their corresponding branched isomers having a higher melting point than their linear isomers.
For example, the n-C16 paraffin has a melting point of 19° C., whilst its 5-methyl pentadecane isomer melts at -31° C.
An effective hydroisomerization catalyst should anyway minimize the possible cracking and hydrocracking reactions, which are catalyzed by the same acidic sites, and have, as intermediates, the same carbocations useful for hydroisomerization. These side reactions cause the degradation of the molecule, with less valuable, ligther products being formed, which must be removed from the end product in order not to increase the volatility thereof; the need for such additional removal step obviously increases the general costs of the overall process. For this process, bifunctional catalysts were developed, catalysts which are provided with both acidic sites and hydro-dehydrogenation active sites. The acidity is given to the catalyst by the type of selected carrier, and its function exactly is supplying the catalysts with such an isomerizing property.
The hydro-dehydrogenating activity is supplied to the catalyst by the deposited metal phase, the function of which is also of keeping cracking reactions to a very minimum.
It was demonstrated (J. F. Le Page, Applied Heterogeneous Catalysis, Ed. Technip, Paris, 1987, 435-466) that, with the hydrogenating activity being the same, the more selective catalysts are those in which the carrier has a controlled acidity, so as to maximize the isomerization of n-paraffins, over cracking reactions. However, inasmuch as the cracking reactions take place after the isomerization reactions, the maximal isomerization selectivity is obtained at low conversion levels (G. Froment et al., Ind. Eng. Chem. Prod. Res. Dev., 1981, 20, 654-660).
The effectiveness of various catalysts can be evaluated on model compounds as n-paraffins, by measuring the selectivity thereof, i.e., the ratio of the isomerization products to the cracking products, at a given level of conversion of n-paraffins.
Among most recent patents, EP-A-321,307 discloses a process for wax hydroisomerization in order to produce lubricant oil bases, which implies a hydroisomerization step carried out in the presence of a particular catalyst. The latter contains from 0.1 to 5% by weight of a metal belonging to Group VI or VIIIA, preferably VIIIA, still more preferably a noble metal of Group VIIIA, in the most preferred form, platinum supported on a halogenated, preferably fluorinated, refractory inorganic oxide.
The halogenation of the inorganic oxide is known to increase the acidity thereof. In particular, the surface acidity of fluorinated aluminas and their catalytic activity in the reactions occurring via carbocation, is a function of their fluorine content (R. Covini, V. Fattore, N. Giordano, J. Catal., 1967, 9, 315-321).
U.S. Pat. No. 4,975,17 discloses a further process for hydroisomerizing waxes, in which provided is a hydroisomerization step carried out in the presence of a catalyst constituted by beta zeolite plus one effective component in hydrogenation-dehydrogenation reaction, preferably a noble metal. This catalyst has a high SiO2 :Al2 O3 ratio, at least equal to 30, preferably higher than 50, for example comprised within the range of from 100 to 500, in order to reduce the acidity thereof and consequently the possible cracking reactions.
As regards the process, both the above cited patents report that wax conversions should be limited to 20-40% by weight, in order to minimize the formation of light products caused by cracking.
The catalyst disclosed in EP-A-321,307 suffers from the drawback that it should be prepared by starting from a highly toxic and corrosive reactant as HF, dissolved in water together with NH4 F.
The process disclosed in U.S. Pat. No. 4,975,177 uses a catalyst in which the beta zeolite is prepared according to as disclosed in U.S. Pat. No. 3,308,069, U.S. Pat. No. 4,419,220 and U.S. Pat. No. 4,518,485. Owing to the low ratio of SiO2 :Al2 O3, typical of this beta zeolite, a de-alumination should be carried out by steaming and/or acidic treatment of the starting zeolite in order to obtain acceptable selectivity. In fact, owing to the high acidity of zeolites, under the hydroisomerization conditions the cracking reaction is very competitive with the isomerization reaction. The de-alumination requires the addition of a further step in the global catalyst synthesis which, with the crystallization being performed under hydrothermal conditions, is, per se, already much more complex than the preparation of an amorphous silica-alumina.
In U.S. Pat. No. 5,049,536, disclosed is an amorphous and microporous silica-alumina gel, active in the processes of isomerization, alkylation, dewaxing and dimerization of linear olefins. Typical characteristics of said material are its high acidity, as compared to conventional amorphous silica-aluminas and the very narrow distribution of its average pore diameter.
The present Applicants found now, according to the present invention, that using a gel of the same type as disclosed in U.S. Pat. No. 5,049,536 as the acidic carrier for limited amounts of metals of Group VIIIA, in particular palladium and platinum, makes it possible a catalyst to be obtained with uniform and controlled porosity, which is effective in paraffin hydroisomerization, also without any treatments with fluorinated compounds.
In accordance therewith, the present invention relates to a bifunctional catalyst comprising:
(a) a carrier of acidic character constituted by an X-ray amorphous silica and alumina gel, with a molar ratio of SiO2 :Al2 O3 comprised within the range of from 30:1 to 500:1, a surface area comprised with the range of from 500 to 1000 m2 /g, with a porosity of from 0.3 to 0.6 ml/g, with a diameter of pores prevailingly comprised within the range of from 10 to 30 Angstroms;
(b) one or more metals belonging to Group VIIIA, in amounts comprised within the range of from 0.5 to 5% by weight.
In preferred embodiment, the acidic carrier of the present invention displays a ratio of SiO2 :Al2 O3 comprised within the range of from 50:1 to 300:1 and a porosity of the order of 0.4-0.5 ml/g, and the noble metal, selected from platinum and palladium, is contained at a level of from 0.1 to 2% by weight.
The silica and alumina gel can be advantageously prepared according to as disclosed in U.S. Pat. No. 5,049,536; in particular, an aqueous solution of a tetra alkyl ammonium hydroxide (TAA-OH), is prepared, in which "alkyl" means ethyl, n-propyl or n-butyl, of a soluble aluminum compound capable of yielding Al2 O3 by hydrolysis, and a soluble silicon compound capable of yielding SiO2 by hydrolysis, with the amount of said constituents in said solution being such that the following molar ratios are complied with:
* SiO2 :Al2 O3 from 30:1 to 500:1;
* TAA-OH:SiO2 from 0.05:1 to 0.2:1;
* H2 O:SiO2 from 5:1 to 40:1;
and the resulting solution is heated in order to cause it to undergo gelation; the resulting gel is dried and is calcined under an inert atmosphere and then under an oxidizing atmosphere.
The metal phase can be added either by impregnation from an aqueous medium, or by ionic exchange.
More particularly, according to the first operating technique, the silica-alumina gel, prepared as disclosed above, is wetted with an aqueous solution of a compound of the selected noble matal, for example chloroplatinic acid or Pd(NH3)4 (NO3)2, by operating at room or close-to-room temperatures, and at a pH value of the order of 1-4 pH units. After aqueous impregnation, the solid material is dried, preferably in air, at room or close-to-room temperatures, and is submitted to a thermal treatment under an oxidizing atmosphere, preferably in air. Suitable temperatures for this thermal treatment are comprised within the range of from 200° to 600° C. The conditions are so adjusted that on silica-alumina particles an amount of noble metal is deposited which is comprised within the range of from 0.05 to 5% by weight, preferably of from 0.1 to 2%.
According to the operating technique based on ionic exchange, the silica-alumina gel is suspended in an aqueous solution of a noble metal complex or salt, for example, an aqueous solution of Pt(NH3)4 (OH)2 or of Pt(NH3)4 Cl2 or of Pd(NH3)4 (NO3)2, by operating at room or close-to-room temperatures, and at a pH value comprised within the range of from 6 to 10. After the ionic exchange the solid matter is separated, then is washed with water, is dried and finally is submitted to thermal treatment in an inert or oxidizing atmosphere. Thermal treatment temperatures comprised within the range of from 200° to 600° C. were found useful. The conditions are so controlled, that an amount of noble metal comprised within the range of from 0.05 to 5% by weight, preferably of from 0.1 to 2%, is deposited on silica-alumina particles.
In any cases, after these ionic exchange or aqueous impregnation operations, bifunctional catalysts are obtained which consist of silica-alumina gel carriers loaded with a noble metal, having in general a surface area comprised within the range of from 300 to 900 m2 /g.
The best results in terms of catalytic activity in the hydroisomerization process are obtained with the catalysts prepared according to the technique of aqueous impregnation, which display high values of paraffin conversion, together with good results of selectivity to isoparaffins.
In the case when one wishes to operate at low paraffin conversion rates, those catalysts are however preferable which are prepared by means of the ionic exchange technique, and, among these, preferably those which contain palladium which, at low conversion rates, display very good selectivities to isoparaffins.
The catalysts according to the present invention can be activated by drying and/or reduction, preferably by drying and subsequent reduction. The drying is carried out in an inert atmosphere at a temperature comprised within the range of from 100° to 400° C., and the reduction is obtained by means of the thermal treatment of the sample under a reducing atmosphere at temperatures comprised within the range of from 150° to 500° C. These steps, which constitute additional steps to the whole process, result to be essential in order to obtain the desired improvement in the performance of the same catalysts, because they increase the selectivity characteristics thereof.
The catalysts according to the present invention can be used as such, or in combination with suitable inert, solid materials acting as binding agents. For that purpose, oxide compounds of the type of silica, alumina, and titanium, magnesium and zirconium oxides, either taken as individual compounds or combined with one another, result to be suitable, The catalyst and the binder can be mixed in mutual ratios, by weight, comprised within the range of from 30:70 to 90:10 and preferably of from 50:50 to 70:30. The above said two components can be bonded and compacted in their end desired shape, for example, as extrudates or pellets. According to an alternative route, the silica-alumina gel based catalyst loaded with a noble metal can be prepared by starting from the acidic carrier which already is an extrudate form. In that case, the carrier, as a silica-alumina gel extrudate prepared according to the process disclosed in Italian patent application MI 91 A 003276 filed on Dec. 6th, 1991 is impregnated with a suitable aqueous solution of noble metal compound, then is dried and submitted to thermal treatment according to the same process as disclosed for the acidic carrier in powder form. These steps can be carried out in a similar way also in the case of the ion exchange process.
The catalyst prepared according to the above reported techniques, as such, or bonded with an inert material, is active in the hydroisomerization process, which can be carried out either continuously or batchwise.
The hydroisomerization is advantageously carried out in the presence of hydrogen, at a temperature comprised within the range of from 200° to 540° C., preferably of from 250° to 450° C., and under a pressure comprised within the range of from 25,000 kPa, preferably of from 4,000 to 10,000 kPa.
The effective catalyst amount, expressed as a percent content, by weight, based on the n-paraffin or mixtures of n-paraffins to be hydroisomerized, is generally comprised within the range of from 0.5 to 30% by weight, preferably of from 1 to 15% by weight.
The following experimental examples are reported in order to better illustrate the present invention.
The material used as the acidic carrier in the catalysts claimed herein, is prepared according to as disclosed in U.S. Pat. No. 5,049,536.
Two grams of aluminum isopropoxide is dissolved at room temperature in 68.5 g of an aqueous solution of tetrapropyl ammonium hydroxide (TPA-OH at 13.35% by weight/weight). The solution is heated up to 60° C. and then 104.1 g of tetraethyl silicate (TES) is added. The resulting mixture displays the following molar ratios:
* SiO2 :Al2 O3 =102,
* TPA-OH:SiO2 =0.09, and
* H2 O:SiO2 =15.
By keeping this mixture with stirring at 60° C. during 40 minutes, a homogeneous gel is formed which is dried under a flowing air stream at 90° C., and then is calcined at 550° C. under a flowing nitrogen stream during 3 hours and subsequently under a flowing air stream during further 10 hours, still at the same temperature.
An X-ray amorphous silica-alumina gel is obtained in a quantitative yield relatively to the initial charged materials.
The so prepared material is used as an acidic carrier on which platinum is deposited by means of an aqueous impregnation.
More particularly, to 10 g of silica-alumina prepared inside a crystallizer, 12.06 ml of, an aqueous solution containing H2 PtCl6 (0.45% by weight/volume and (0.6M) HCl is added dropwise, with simultaneously carefully mixing. The reactants are kept into contact with each other for 16 hours, then water is evaporated off during 1 hour at the temperature of 60° C. in air and the sample is subsequently dried, during 2 hours, at 150° C., still in air. The calcination is carried out at 500° C. for 3 hours under a flowing air stream, with the muffle being heated from 23° to 500° C. during a 90 minutes time.
The catalyst characterization data are reported in Table 1.
The process is carried out with a carrier as from Example 1, by performing the metal phase deposition step by means of the ion exchange method.
To 10 g of amorphous silica-alumina, 80 ml of an aqueous solution of Pt(NH3)4 Cl2 (0.06% of Pt by weight/volume) and some drops of NH4 OH at 35% by weight, such as to alkalify this suspension at pH=9, are added. The resulting mixture is kept with stirring at room temperature for 1 hour, then is filtered and the filter cake is washed with water. After a 16-hour drying at 110° C. in air, the sample is calcined for 3 hours at 400° C. under a flowing air stream, with a temperature increase ramp of from 23° to 400° C. during 30 minutes.
The characteristics of the catalyst are reported in following Table 1.
A catalyst is prepared by starting from a same carrier as from Example 1, by performing the metal phase deposition step by means of the ion exchange method.
Then grams of carrier as disclosed in Example 1 is added, with stirring at room temperature, to 1000 ml of demineraliized water. 27.23 ml of Pd(NH3)4 (NO3)2 (0.01M) and some drops of NH4 OH at 35%, such as to increase the suspension pH up to about 6, are added; the resulting mixture is kept with stirring for 3 hours at room temperature. The resulting suspension is filtered, the filter cake is washed with water and is allowed to dry at room temperature. The drying takes place at a temperature of 80° C. in air for 3 hours, and the calcination is carried out at 250° C. for 3 hours, under a flowing air stream.
The characteristics of this catalyst are reported in Table 1.
A catalyst is prepared by starting from a same carrier as from Example 1, by performing the metal phase deposition step by means of the aqueous impregnation method.
A volume of 12.06 ml of an aqueous solution of Pd(NH3)4 (NO3)2 (0.005M) is added dropwise to 10 g of the same carrier as obtained from Example 1. The subsequent impregnation steps are carried out as in Example 1. The calcination is carried out at 250° C. during 3 hours under a flowing air stream with a temperature increase rate of 7° C./minute.
The characteristics of this catalyst are reported in Table 1.
A reference catalyst is prepared which is constituted by platinum supported on beta zeolite.
Said beta zeolite is prepared under similar conditions to as disclosed i n U.S. Pat. No. 3,308,069.
An amount of 59.8 g of an aqueous solution at 40% by weight/weight of tetraethylammonium hydroxide (TEA-OH) and 1.9 g of sodium aluminate are added to 58.4 g of demineralized water. The resulting mixture is heated up to about 80° C. and is kept with stirring until NaAlO2 is completely dissolved. The resulting solution is added to 48.7 g of colloidal silica Ludox HS at 40% by weight, such as to yield a molar ratio of SiO2 :Al2 O3 =28.
The resulting homogeneous suspension, having pH=14, is charged to a stainless steel autoclave and is caused to crystallize under hydrothermal conditions in an oven at 150° C. during a 10-day time, under static conditions, under the autogenous pressure.
The crystallized product is filtered off, the filter cake is washed, is dried for 1 hour at 120° C., is calcined during 5 hours at 550° C. and is turned into its acidic form by exchange with ammonium acetate and subsequent calcination under the above indicated conditions.
The Pt metal phase is deposited on the beta zeolite by aqueous impregnation.
In particular, on 10 g of beta zeolite, 12.06 ml of an aqueous solution containing H2 PtCl6 (0.45% Pt by weight/volume) and HCl (0.6M) is added dropwise, with careful mixing. The subsequent impregnation, drying and calcination steps are as disclosed in Example 1.
The characteristics of the resulting catalyst are reported in Table 1, in which "SiO2 :Al2 O3 " indicates the molar ratio of silica to alumina, and "Pore dm " indicates the average diameter of the pores, expressed as Angstrom.
TABLE 1 ______________________________________ Metal Surface Pore Pore % area SiO.sub.2 :Al.sub.2 O.sub.3 volume d.sub.m Cat. w/w (m.sup.2 /g) (m/m) (mL/g) (A) ______________________________________ Ex. 1 0.52 674.6 100 0.44 <30 Ex. 2 0.58 496.3 100 0.44 <30 Ex. 3 0.27 485.9 100 0.44 <30 Ex. 4 0.25 590.4 100 0.44 <30 Ex. 5 0.51 626.3 28.3 0.75 7.5 × 5.7 6.5 × 5.6 ______________________________________
The catalyst from Example 1 was tested in the reaction of hydroisomerization of n-C16 paraffin, in a microautoclave, under the following conditions.
The microautoclave is constituted by a steel body and a cover provided with a plurality of valves for pressurization, venting and optional recovery of gas products, and a pressure relief disk. The stirring system is constituted by a thin internal metal rod.
The reactor is charged with 8 g of C16 paraffin and 0.25 g of catalyst; the system is pressurized when cold with H2 at 5 MPa and then is heated up to the temperature of 360° C.
As zero time, the point in time is considered when the temperature inside the reactor interior reaches the desired value. After 120 minutes, the reactor is cooled and the internal pressure thereof is relieved, and the reaction mixture is recovered. The analysis of the products in order to determine the conversion and their distribution is directly carried. out on the mixture, by gas chromatography (crosslinked methyl silicone gum HP-1 column, atomic emission detector).
In Table 2, the values of conversion and selectivity are reported, which were computed as follows: ##EQU1## in which "iso-C16 " is the mixture of isomers containing 16 carbon atoms, and "C16 --" is the mixture of cracking products, with less than 16 carbon atoms.
A catalyst according to Example 2 is tested in the hydroisomerization of n-C16 paraffins. The reaction conditions are the same as in Example 6. The values of conversion and selectivity are reported in Table 2.
A catalyst according to Example 3 is tested in the hydroisomerization of n-C16 paraffins. The reaction conditions are the same as in Example 6. The values of conversion and selectivity are reported in Table 2.
A catalyst according to Example 2 is tested in the hydroisomerization of n-C16 paraffins. The reaction conditions are the same as in Example 7, except for the reaction time being extended to 240 minutes. The values of and selectivity are reported in Table 2.
TABLE 2 ______________________________________ Selectivity to Selectivity to Example Conversion % iso-C.sub.16 C.sub.16 - ______________________________________ 6* 79.5 87.29 12.70 7* 19.0 94.48 5.52 8* 25.5 96.39 3.61 9+ 26.3 95.67 4.33 ______________________________________ Reaction conditions: T = 360° C., P.sub.H2 = 5 MPa, nC.sub.16 :catalyst = 8:0.25; *time = 120 minutes; +time = 240 minutes.
From Examples 6 and 7, one may observe how the metal phase deposition method has an influence on the conversion rate, with the operating conditions being the same. From Examples 8 (Pd containing catalyst) and 9 (Pt containing catalyst), one may observe that the hydrogenating function performed by palladium supplies the system with a slightly better hydroisomerizing performance than with platinum.
The processes described in technical literature for the hydroisomerization of waxes (e.g., U.S. Pat. No. 4,975,177 and EP-A-321,307) limit the conversion rates to values comprised within the range of from 20 to 40% by weight, in order to keep the cracking byproducts to their minimum; the catalysts from Examples 2 and 3 displayed such catalytic activities, which made it possible the resulting conversion rates to fall within the range taken into consideration, with extremely good selectivity values to iso-C16 products.
The catalyst taken as the reference catalyst (Example 5) is tested in the hydroisomerization of n-C16 paraffins. The reaction conditions are the same as in Example 6. The conversion rate and selectivity values are reported in Table 3.
The catalyst taken as the reference catalyst (Example 5) is tested in the hydroisomerization of n-C28 paraffins. The reaction conditions are the same as in Example 6. The conversion rate and selectivity values are reported in Table 3.
A catalyst according to Example 1 is tested hydroisomerization of n-C28 paraffins. The reaction conditions are the same as in Example 11. The values of conversion rate and selectivity are reported in Table 3.
TABLE 3 ______________________________________ Selectivity to Selectivity to Example Conversion % iso species cracked species ______________________________________ 6* 79.5 87.29 12.7 10* 86.0 13.26 86.7 11+ 98.1 / 100 12+ 61.2 94.12 5.89 ______________________________________ Reaction conditions: T = 360° C., t = 120 minutes, P.sub.H2 = 5 MPa, substrate:catalyst = 8:0.25. *substrate = nC.sub.16 ; +substrate = nC.sub.28
From the tests of the Examples 6, 10, 11 and 12, it was verified that the catalysts according to the present invention (Examples 6 and 12) display a higher hydroisomerization selectivity, in the hydroisomerization of both n-C16 and n-C28 paraffins, with the operating conditions being the same, as compared to a catalyst taken as the reference catalyst (Examples 10 and 11).
A catalyst as from Example 1, is tested in the hydroisomerization of n-C16 paraffins. The reaction conditions are kept equal to those as of Example 6 in order to verify the reproducibility of the process. The values of conversion rate and selectivity are reported in Table 4.
A catalyst as from Example 1, is first dried in an N2 atmosphere at 300° C. and is subsequently tested in the hydroisomerization of n-C16 paraffins. The reaction conditions are the same as of Example 6. The values of conversion and selectivity are reported in Table 4.
A catalyst as from Example 1, is first activated under a H2 atmosphere at 400° C. and is subsequently tested in the hydroisomerization of n-C16 paraffins. The reaction conditions are the same as of Example 6. The values of conversion rate and selectivity are reported in Table 4.
A catalyst as from Example 1, is first activated as in Example 15 and is subsequently tested in the hydroisomerization of n-C16 paraffins. The reaction conditions are the same as of Example 15, except for the reaction time, which is reduced down to 60 minutes. The values of conversion and selectivity are reported in Table 4.
TABLE 4 ______________________________________ Selectivity to Selectivity to Example Conversion % iso-C.sub.16 C.sub.16 - ______________________________________ 6 79.5 87.29 12.7 13 79.4 86.52 13.48 14 72.0 89.03 10.97 15 72.2 90.44 9.56 16* 39.8 89..45 10.55 ______________________________________ Reaction conditions: T = 360° C., T = 120 minutes, P.sub.H2 = 5 MPa, nC.sub.16 :catalys = 8:0.25; t = 60 minutes.
From Examples 6 and 13, the extremely good reproducibility of the reaction system emerges.
From Examples 6, 14 and 15 one may observe that, against a yield decrease of 8% by weight, the selectivity ratio of iso-C16 :C16 -- is favoured by an activating treatment, in particular by a reducing treatment (Example 15).
From Examples 15 and 16, it may be observed that halving the test time actually causes decrease in conversion rate, with the selectivity to iso-C16 products remaining nearly constant.
Claims (3)
1. Process for hydroisomerizing n-paraffins containing more than 15 carbon atoms, characterized in that the n-paraffin, or a mixture of n-paraffins, is brought into contact, under hydroisomerization conditions, with a bifunctional catalyst comprising:
(a) a carrier of acidic character constituted by silica-alumina gel, amorphous as determined by X-ray analysis, with a molar ratio of SiO2 :Al2 O3 comprised within the range of from 30:1 to 500:1, a surface area comprised within the range of from 500 to 1,000 m2 /g, with a porosity comprised within the range of from 0.3 to 0.6 ml/g, with a diameter of pores comprised within the range of from 10 to 30 Å;
(b) one or more metals belonging to Group VIIIA, in amounts comprised within the range of from 0.05 to 5% by weight.
2. Process for hydroisomerizing n-paraffin according to claims 1, characterized in that said process is carried out in the presence of an amount of bifunctional catalyst comprised within the range of from 0.5 to 30% by weight, based on n-paraffins, at a temperature comprised within the range of from 200° to 540° C., and under a hydrogen pressure comprised within the range of from atmospheric pressure up to 25,000 kPa.
3. Process according to claim 2, characterized in that it is carried out in the presence of a bifunctional catalyst used in an amount comprised within the range of from 1 to 15% by weight based on n-paraffins, at a temperature comprised within the range of from 250° to 450° C., and under a hydrogen pressure comprised within the range of from 4,000 to 10,000 kPa.
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US08/519,759 Expired - Lifetime US5767038A (en) | 1992-07-31 | 1995-08-28 | Catalyst for the hydroisomerization of long-chain N-paraffins and process for preparing it |
US09/064,004 Expired - Fee Related US5968344A (en) | 1992-07-31 | 1998-04-21 | Catalyst for the hydroisomerization of long-chain n-paraffins and process for preparing it |
Country Status (9)
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US (3) | US5602292A (en) |
EP (1) | EP0582347B1 (en) |
JP (1) | JP4103053B2 (en) |
AT (1) | ATE142906T1 (en) |
DE (1) | DE69304840T2 (en) |
DK (1) | DK0582347T3 (en) |
ES (1) | ES2092217T3 (en) |
GR (1) | GR3021322T3 (en) |
IT (1) | IT1256084B (en) |
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US5968344A (en) * | 1992-07-31 | 1999-10-19 | Eniricerche S.P.A. | Catalyst for the hydroisomerization of long-chain n-paraffins and process for preparing it |
US6071485A (en) * | 1996-06-13 | 2000-06-06 | Eniricerche S.P.A. | Process for the preparation of a micro-meso porous material with a high surface area and controlled distribution of the porosity |
US6274540B1 (en) | 1997-07-21 | 2001-08-14 | The Procter & Gamble Company | Detergent compositions containing mixtures of crystallinity-disrupted surfactants |
US6303556B1 (en) | 1999-01-20 | 2001-10-16 | The Procter & Gamble Company | Hard surface cleaning compositions comprising modified alkybenzene sulfonates |
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US20020103096A1 (en) * | 1997-07-21 | 2002-08-01 | Kott Kevin Lee | Alkylaryls |
US20020183576A1 (en) * | 2001-04-12 | 2002-12-05 | Snamprogetti S.P.A. | Process for obtaining a "diesel cut" fuel by the oligomerization of olefins or their mixtures |
US6525233B1 (en) | 1997-08-08 | 2003-02-25 | The Procter & Gamble Company | Process for preparing a modified alkylaryl |
US6566319B1 (en) | 1997-07-21 | 2003-05-20 | The Procter & Gamble Company | Cleaning products comprising improved alkylarylsulfonate surfactants prepared via vinylidene olefins and processes for preparation thereof |
US6593285B1 (en) | 1997-07-21 | 2003-07-15 | The Procter & Gamble Company | Alkylbenzenesulfonate surfactants |
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US20030171631A1 (en) * | 2000-05-19 | 2003-09-11 | Cristina Flego | Solid base catalyst and use thereof in base catalysis |
US6638888B1 (en) * | 1995-06-15 | 2003-10-28 | Eniricerche S.P.A. | Mesoporous alumina gel and process for its preparation |
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US3637484A (en) * | 1970-06-18 | 1972-01-25 | Union Oil Co | Platinum group metal on silica-alumina hydrogenation catalyst and process |
US3855347A (en) * | 1972-09-15 | 1974-12-17 | Badger Co | Process for hydrogenating halogenated hydrocarbons |
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US5139989A (en) * | 1991-08-28 | 1992-08-18 | Uop | Amorphous silica/alumina/phosphate composition and uses thereof |
IT1256084B (en) * | 1992-07-31 | 1995-11-27 | Eniricerche Spa | CATALYST FOR THE HYDROISOMERIZATION OF NORMAL-LONG CHAIN PARAFFINS AND PROCEDURE FOR ITS PREPARATION |
IT1255526B (en) * | 1992-09-29 | 1995-11-09 | Eniricerche Spa | PROCEDURE FOR THE PREPARATION OF AN EFFECTIVE CATALYST IN THE NORMAL-PARAFFIN HYDROISOMERIZATION |
IT1264031B (en) * | 1993-04-08 | 1996-09-09 | Eniricerche Spa | PROCESS FOR THE PRODUCTION OF PETROL AND JET FUEL STARTING FROM N-BUTANE |
IT1264423B1 (en) * | 1993-05-12 | 1996-09-23 | Eniricerche Spa | BIFUNCTIONAL HARDENER USEFUL IN THE HYDROISOMERIZATION OF WAXES AND PROCEDURE FOR ITS PREPARATION |
IT1264626B1 (en) * | 1993-06-16 | 1996-10-04 | Eniricerche Spa | PROCESS FOR THE PREPARATION OF CUMENE |
IT1265320B1 (en) * | 1993-12-22 | 1996-10-31 | Eniricerche Spa | PROCEDURE FOR THE PREPARATION OF CATALYTICALLY ACTIVE AMORPHOUS SILICON-ALUMIN |
-
1992
- 1992-07-31 IT ITMI921895A patent/IT1256084B/en active IP Right Grant
-
1993
- 1993-07-30 JP JP20854493A patent/JP4103053B2/en not_active Expired - Fee Related
- 1993-07-30 DK DK93202253.6T patent/DK0582347T3/da active
- 1993-07-30 AT AT93202253T patent/ATE142906T1/en not_active IP Right Cessation
- 1993-07-30 DE DE69304840T patent/DE69304840T2/en not_active Expired - Lifetime
- 1993-07-30 ES ES93202253T patent/ES2092217T3/en not_active Expired - Lifetime
- 1993-07-30 EP EP93202253A patent/EP0582347B1/en not_active Expired - Lifetime
-
1995
- 1995-05-25 US US08/449,957 patent/US5602292A/en not_active Expired - Lifetime
- 1995-08-28 US US08/519,759 patent/US5767038A/en not_active Expired - Lifetime
-
1996
- 1996-10-10 GR GR960402685T patent/GR3021322T3/en unknown
-
1998
- 1998-04-21 US US09/064,004 patent/US5968344A/en not_active Expired - Fee Related
Patent Citations (1)
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US5049536A (en) * | 1988-05-06 | 1991-09-17 | Eniricerche S.P.A. | Catalytically active silica and alumina gel and process for preparing it |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5968344A (en) * | 1992-07-31 | 1999-10-19 | Eniricerche S.P.A. | Catalyst for the hydroisomerization of long-chain n-paraffins and process for preparing it |
US6638888B1 (en) * | 1995-06-15 | 2003-10-28 | Eniricerche S.P.A. | Mesoporous alumina gel and process for its preparation |
US6071485A (en) * | 1996-06-13 | 2000-06-06 | Eniricerche S.P.A. | Process for the preparation of a micro-meso porous material with a high surface area and controlled distribution of the porosity |
US6566319B1 (en) | 1997-07-21 | 2003-05-20 | The Procter & Gamble Company | Cleaning products comprising improved alkylarylsulfonate surfactants prepared via vinylidene olefins and processes for preparation thereof |
US20020103096A1 (en) * | 1997-07-21 | 2002-08-01 | Kott Kevin Lee | Alkylaryls |
US6593285B1 (en) | 1997-07-21 | 2003-07-15 | The Procter & Gamble Company | Alkylbenzenesulfonate surfactants |
US6602840B1 (en) | 1997-07-21 | 2003-08-05 | The Procter & Gamble Company | Processes for making alkylbenzenesulfonate surfactants and products thereof |
US6274540B1 (en) | 1997-07-21 | 2001-08-14 | The Procter & Gamble Company | Detergent compositions containing mixtures of crystallinity-disrupted surfactants |
US6908894B2 (en) | 1997-07-21 | 2005-06-21 | The Procter & Gamble Company | Alkylaromatic hydrocarbon compositions |
US6525233B1 (en) | 1997-08-08 | 2003-02-25 | The Procter & Gamble Company | Process for preparing a modified alkylaryl |
US6342473B1 (en) | 1999-01-20 | 2002-01-29 | The Procter & Gamble Company | Hard surface cleaning compositions comprising modified alkylbenzene sulfonates |
US6303556B1 (en) | 1999-01-20 | 2001-10-16 | The Procter & Gamble Company | Hard surface cleaning compositions comprising modified alkybenzene sulfonates |
US20030171631A1 (en) * | 2000-05-19 | 2003-09-11 | Cristina Flego | Solid base catalyst and use thereof in base catalysis |
US7341973B2 (en) | 2000-05-19 | 2008-03-11 | Polimeri Europa S.P.A. | Solid base catalyst and use thereof in base catalysis |
US20020183576A1 (en) * | 2001-04-12 | 2002-12-05 | Snamprogetti S.P.A. | Process for obtaining a "diesel cut" fuel by the oligomerization of olefins or their mixtures |
US6914165B2 (en) | 2001-04-12 | 2005-07-05 | Snamprogetti S.P.A. | Process for obtaining a “diesel cut” fuel by the oligomerization of olefins or their mixtures |
Also Published As
Publication number | Publication date |
---|---|
ITMI921895A0 (en) | 1992-07-31 |
IT1256084B (en) | 1995-11-27 |
DK0582347T3 (en) | 1997-02-24 |
US5968344A (en) | 1999-10-19 |
DE69304840T2 (en) | 1997-03-20 |
EP0582347B1 (en) | 1996-09-18 |
JPH06170226A (en) | 1994-06-21 |
ES2092217T3 (en) | 1996-11-16 |
DE69304840D1 (en) | 1996-10-24 |
JP4103053B2 (en) | 2008-06-18 |
GR3021322T3 (en) | 1997-01-31 |
US5767038A (en) | 1998-06-16 |
ATE142906T1 (en) | 1996-10-15 |
ITMI921895A1 (en) | 1994-01-31 |
EP0582347A1 (en) | 1994-02-09 |
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